Vat dyestuff derived from anthraquinone and process of making same



Patented Nov. 28, 1922.

UNITE srm'es 1,436,770 PATENT OFFICE.

BEBTRAM MAYER, WILHELM MOSEB, AND .T-AKOB Wfi'EGLER, 01 BASEL, SWITZER-LAND, ASSIGNOBS TO SOCIETY OF CHEMICAL-INDUSTRY IN BASLE, OF BASEL,

SWITZERLAND.

VAT DYESTUFF DERIVED FROM ANTHRAQUINONE AND PROCESS OF MAKING SAME.

No Drawingv To all :whom it may concern:

it known that we, BERTRAM MAYER,

citizen of the German Republic, WiLHnLM Mosnn, citizen of the GermanRepublic, and JAKOH Wtinemin, citizen of the Swiss Republic, nll threeresidents of Basel, Switzerland, have invented new and useful VatDyestuffs Derived from Anthraquinone and Processes of Making Some, ofwhich the f0llowing is a'full, clear, and exact specifica' tion.

These bodies are dark-brown powders g ing with hydrosulfite and causticsoda rats having only a feeble allinity for vegetable fibres. Theirindustrial value lies in the 'fact thatthey can be condensed easily withort'ho-diuniiino-unthraquiuonee to rut-(lyestuffs the constitutionwhereof is characterized by the presence of at least one anthrmquinonealphabeta. naphthazine complex united by a N--H group to un' anthroqum-Application filed February 1, 1922. Serial No. 533,352.

&1

one nucleus" which can bear (Itl11.Slll)SlZlt- 30 ucnte, one of thenitrogen rnlences of the N--ll grou p1,- being fixed in any position tothe naphthalene nucleus of the anthraiquinone-ulphabeta-uaphthazines andthe other to one of the alpha positions of the second anthraquinonenucleus, as shown by the lowing formulas illustrating particular casesof ourvim'ention.

These new vat dyestl'lfis are in a, red powders.

8 1d dissolvgvin a m c audio 11.. green coloratign. ith caustlcyrh'osndfite the more or less dark 5 man and' h g be dyegl red to violettints of ing examples: 1o

anthraquinone, 40

salt of the betanap tho acid and100 boiled fdrrhal aLn withareflu;Ooolerparts of hot water 15 still bqiled or ay'fe filtration theliesjdue is' until complete dlsa pp'ea and dried. Themls red powdf whiahdisso w tbluene and xy1ene,m0m 26 zene. Ftomitq sqluticy Ewamplq 1. Amixturepf 20 parts of alphar'aminm arts of the 4p0tas3ium parts of g'none- -sulfon-ic to;'the b l acetic midis in-m avessalprovidgd and asth rer, than are guided land the whole w moments. Aftpr mashed with,we; b MOB of acetic acid thus ohm state 'l h h are 've' reddishpottoncan flocky The mvention-isillustrated y the follow-- ined in. brownd1lvea diflicultly in easily in-nitrobendiluted in nih'gbeuzene theproduct can be form of fine b solves in conoent low-brown solut tionwith yvajae VGIIY feebl O boils? quinone and 5 ma's is'then cool rownishred ficulfly in nitr wolves in fu furic gcidfo I obtained cl ystallizedin the wn red needles. It'disrated Sulfuric acid to a, yelion; by dilutithen; is pro used 0 afilnity fpr cotton. rts bf-this condensation artsof 2.8-diammo-anthw as parts of nitrobenzene, the

ed down a; lacial acetic acid are previously with alcohol sin newdyestuif thus obtaine ves with by 'added thereof the whole is th donstitu a v o'wder which dissolves if- 45 na to a red solution. It

n coloration giv' th water a'red fl .The new dyestulf g1 l itatz. osulfite and so caustic soda a red-brown vat by means of which cotton can bedyed Bordeaux-red tints of excellent fastness.

Emwmple 2.

A mixture of l i parts of 3-bromo-betanaphthoquinone fi parts ofalpha-aminounthraquinone, 8 parts of anhydrous sodium acetate, 5 part.of copper chloride and 20o arts of glacial acetic acid is boiled for (iours in a vessel provided with a reflux cooler. After cooling the massis filtered. The residue is washed copiously with hot water and dried.There is thus obtained a brown powder of cr 'stalline appearance whichdis solves diflicultly in toluene and xylene, more easily innitrobenzene. From its solution in nitrobenzene the product can becrystallized in form of fine, brown-red needles. It dis solves inconcentrated sulfuric acid to a 7 solution of the vat obtained Fll'stcomponent. a Second component. Third component. dycstufi in Sup 1 Wm hedyer L 1u sluil iuric 'aci d stutl'. ,A an nnfl. fi. nkiunpnnmnl 4 .n nM... Bota-naphthoquinnne- Alphaamino anthra 1.2. (li niino anthraqui-Green Red-brown Bluish Bordeaux.

i-sultonic acid 1 mol. qulnone 1 mol. none 1 moi. c A An? n ditto...bamino-A-mcthoxy- ..,.ditto v litto .....ditl.u .,i Violet.

snthraqulnone 1 mol. i n... We, n... ditto ..dltto 2.3 diaminoanthraquiditto ditto eliotrope.

none l moi. M -1M. A .n M n 4. n n.-in

l ditto l amino fi-chlor an .....llitto ..ditto .uittn Hi Bordeaux.thraquinone 1 mol. in i. .n. fin. .47.... n 6- bromo betanaph Alplmamino anthra- .....d.itto Olive green... ..ditto Red.

thoquinone 1 mol. quinonc 1 mol. .n in .n in. #7 .W. 4.... ditto ..ditto1.2.dinmino-anthraqui- .....ditto ..l. ...[mm iul h Bordeaux.

none 1 niol. 1 I n WW... A. W"-.. I. A- A 7 4-. Beta-naphtha uinone- 1.5diamiim anthra 2.3 lifinnino anlhm Green ditto Ditto d sullonlc mi 2mol. quinone 1 mol. quinonc 2 mol.

. ".7. Wei. n n .Jfln .-A 3 hromo beta naph- .ditto ..(lltl0 ..i1itio.dittu Bluish ted.

thoquinone 2 mol. E

The G-bromo-betanaphthoquinonc used parent. material for the preparationof certain dyestufi's of the tabular exhibit can be prepared easily byapplying the method of transforming l-broino-betana )hthol into btanahthoquino-ne, describe in Justus Llebig's Annalen der Chenne, vol. 389,

pages 315 to 317, to the l-(i-dibromo-bctanaphthol melting at 106mentioned in the Berichte der deutschen chemischen Gesellschaft" No. 24,vol. 3, page 705.

What we claim is: I

1. The herein described process for the manufacture of new vat dyestuffsconsisting in condensing first a derivative of betanaphthoquinonecontaining removable subyellow-brown solution; when this solution isdiluted with water, there is obtained a iiocky red precipitate. Theproduct gives with hydrosulfite and caustic soda a red vat showing avery feeble affinity for cotton.

liy reacting with this product on 2.3-dianiinoanthraquinone in themanner dc scribed in the foregoing example there is obtained a newdyestufi' constituting in a dry state, a red powder which dissolvesrather diilicultly in hot nitrobenzene and more easily in concentratedsulfuric acid with green coloration. it gives with hydrosulfite andcaustic soda, a red-brown rat by means of which cotton can be dyed red-Bordcaux tints oi excellent fastncss.

The following tabular exhibits shows the composition and the propertiesof some dyestufis of our invention. which are all red powders Colorationof thei Coloration oi thoi Tint S Ohmimd in condensing afterwards theresulting product of condensation with 2.3-

iaminoanthraquinone.

4, The h naphthoquinone containing removable substituentsaaminoanthraquinone and in condensing afterwards the resulting productof condensation with 2.3-diaminoanthraquinone.

5. The herein product of condensation with 2.3-diaminoanthraquinone.

6. The herein described new vat dyestuffs resulting from the actionquinone and whose constitution is characresence of at least oneanthraquinone-alp abeta-naphthazine complex united by a N-H group to ananthraquinone nucleus which may bear other substituents, one of thenitrogen valences of the N-H groups being fixed in any position of thenaphthalene nucleus of the anthraquinone-alphabeta-naphthazines and theother in alphaposition of the anthraquinone nucleus, the said dyestuffsbeing, in a dry state, red powders more or less brownish, soluble insulfuric acid to and hydrosulfite brown-red vats by means red to violetized by the presence of an anthraquinonealphabeta-naphthazine complexunited by a N-H group to an anthroquinone nucleus which may bear othersuhstituents, one of the nitrogen valences of the NH group being fixedin any position of the naphthalene nucleus of theauthraquinonealphabetanap thazine and the other in alphaposition of theanthraquinone nucleus, the said dyetic soda and hydrosulfite brown-redvats b means of which cotton can be dyed red to violet tints.

8. The herein described new vat dyestufi's g soluble in sulfuric acid toa soluble in resulting from the action of a 2.3-diam1noanthratgiinone onthe product of condensation of a etanaphthoquinone containing removablthraquinone and whose constitution is characterized by the quinonealphabets -1naphthaz1ne united by a N group to an anthraquinone nucleuswhich may bear other substituents, one of the nitrogen valences of theN- group being fixe in airy position of the naphthalene nucleus of thequinone-alphabeta-naphthazine and the other in alphaposition of theanthraq-uinone nucleus, the said dyestuffs being, in a dry state, redpowders more or less brownish, on solutions with dilute caustic soda andbydrosulfite rown-red rats by means of which cotton can be dyed red toviolet tints.

9. The herein described new vat dyestufl's resulting from the action of2.3-diaminoanthra uinone on the product of condensation ofila b complexand givin etanaphthoqumone containin remova e substituents with themonoalp aaminoanthraquinone's a 'd whose constitution is characterized bto presence of an anthraquinone alphal ieta naphtha zine complete unitedby a N H group to an anthraquinone nucleus which may bear othersubstituents, one of the nitro en valences of the NH group being fixedin any position of the naphthalene nucleus of theanthraquinone-aIphabeta-naphthazine andv the other in alphaposition ofthe anthraquinone nucleus, the said dyestuffs being, in a dry state, redpowders more or less brownish, sulfuric 'aeid to green solutions andgiving with dilute caustic soda, and hydrosulfite b by means of whichcondensation of betanaphthoquinone4- fonio acid with ose constitution ischaracterized b the presence of an anthraquinone alpha eta naghthazinecomplex united by a N-H group to an anthraquinone nucleus which may bearother substituents, one of the nitrogen valences of the N-H group beingfixed in the -position of the naphthalene nucleus of theanthraquinone-alphabeta-napthazine and the other in alpha-position ofthe anthraquinone nucleus, the said dyestuffs being, in a dry state, redpowders more or less brownish, soluble in sulfuric acid to greensolutions and giving with dilute caustic soda. and hydrosulfite by meansof which cotton can be dyed red to violet tints.

11. As a new article of manufacture the iii herein described vatdyestufi resulting from the action of 2.3-diaminoanthraquinone on theproduct of condensation of betanaphthoquinone-4-sult'onic acid withalpha-aminoanthraquinone and. whose constitution is characterized by thepresence of one anthraquinone alphubeta naphthazine complex united by aN-H group to an anthraquinone nucleus, oneof. the valence of thenitrogen group N-H being fixed in a 4- position of the naphthalenenucleus of the anthraquinone alpha beta napthazine and the other in analpha-position of the anthraquinone nucleus the said dyestuil hem? in adry state a red powder, soluble in sul uric acid to a green solution andgiving with caustic soda and hydosulfite a brown-red vat by means ofwhich cotton can be dyed Bordeaux tints.

In witness whereof We have hereunto signed our names this 13th da ofJanuary,

1922, in the presence of two su scribing witnesses.

BERTRAM MAYER. WILHELM MOSER. J AKOB' WURGLER Witnesses:

FRIDK. Russ, AMAND BITTER.

